Catalytic treatment of vapors



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@A'IFLYTIC TREATMENT 0F WPM@ Vanderveen' Voorhees, Homewood, El., assigner to Standard 011 Company, hlcago, mi., a corpo-f ration o! Indiana Implication October 19, 1940, Serial No. 36ll,94l9

(Cl. 19E-52) 8 Claims.

'This invention relates to a process of converting hydrocarbon oils into high knock rating gasoline and particularly to the conversion of petroleum gas oil and heavy naptha of low knock rating into high mock rating gasoline by vapor phase contact with powdered solid contact catalysts suspended therein. The catalysts employed are of the refractory, heterogeneous type in the form of iine granules or powder capable ot being suspended in the hydrocarbon vapors.

One object of the invention is to eect more uniform contacting conditions between the catalyst and the hydrocarbon vapors and particularly to eect a more uniform time of contact or catalyst residence time with catalyst particles oi diderent sizes in a powdered catalyst cracking system wherein the catalyst is suspended in an upflow stream of hydrocarbon vapors at conversion temperatures.

In one oi its broad aspects my invention contemplates the separation of the powdered catalyst trom the vapors in a series of stages, allowing the smaller particles to remain suspended in the vapors in successive contact stages, thereby compensating for the unequal time oi? contact between small and large particles as the result of di'erences in sedimentation rate in the initial contacting zone where retarded settling of the catalyst is provideda 'The invention is illustrated by the accompanyim drawing which shows diagrammatlcally the layout of a plant for converting hydrocarbon oils in two contacting stages.

Referring to the drawing, iced stock which may be Mid-Continent gas oil with a boiling range of about 550 to 800 F. enters the system through line it and is forced by pump ll through pipe heater l2, thence by transfer line it to catalyst mixer it and thence by line it to the rst reaction chamber it. Steam may be introduced to reduce coke deposition on the catalyst.

Catalyst from supply hopper il enters mixer lil by gravity ow, for example, from a standplpe tower to enhance pressure of catalyst, or by mechanical metering device lla and is dispersed in the stream ol oil vapors in transfer line it. The temperature oi the vapors leaving the iurnace il may be of the order of 800 to 1050 F., a suitable temperature for the reaction being about 900 to 950 F. If the powdered catalyst from Ill is supplied in a heated condition, it is not necessary to preheat the vapors in furnace l2 to the extent necessary when the catalyst is supplied at a lower temperature. The amount of catalyst added may be about 1/2 to 10 times the weight of the oil treated although in general the weight ratio of catalyst to oil is about 2 to 5.

The catalyst supplied by hopper il may be a natural earth or clay, generally specially activated by treatment with acid, etc. or it may be dit synthetically prepared, ior example, by precipitation of sodium silicate with acids, precipitation of aluminum salts with ammonium oxide, etc.

Silica gel promoted with alumina, magnesia orr other metal oxide is very satisfactory. In order to handle the catalyst in suspension, it is sometimes necessary to subject it to grinding to obtain the desired degree of neness. In general, the catalyst which I employ will have a iineness such that substantially all will pass a 50 mesh screen and much of it will pass successively through screens of 100, 200, 300 and 400 mesh. In my process I make no effort to grade the catalyst to a uniform particle size but prefer to employ commercial grades of activated or acid treated clays, silica, silicates. such as aluminum silicate, 'alumina-silica mixtures, kieselguhr, silica gel, silica gel activated with alumina or magnesia, etc., ground sufiiciently ilne to remain suspended in the vapor stream during reaction.

The hydrocarbon vapors and suspended catalyst enter the reactor it near the bottom and ow upwardly to the outlet it. In the reactor, temperatures are held at or near the desired conversion temperature, for example, 935 l, and conversion of the hydrocarbons in the vapors is rapidly eected by employing a sufficiently large volume in the reaction chamber and sufficiently log vapor velocity to provide the desired contact t e.

The velocity oi the vapors passing upwardl through chamber it is maintained sumciently to hold in suspension both coarse and ne particles of catalyst while aording relative sedimentation. A vapor velocity of about 2 to 5 feet per second is usually sumcient although higher or lower velocities may be employed. For example, velocities of V2 to 25 feet per second may be emplayed, depending to -a considerable extent on the density and other properties of the catalyst, the size of the catalyst particles and density of the hydrocarbon vapors passing through the reaction chamber.

From the reaction chamber the products are conducted by line it to the coarse catalyst separator it. This separator may be of the cyclone or centrifugal type with tangential inlet providing a swirling motion for the gases therein. Conditions in separator l@ are regulated to separate a fraction of the catalyst having the larger particles and the separated catalyst passes through valve @il into collector 2i from where it is conducted by line 22 to be regenerated. For this purpose, it may be carried by means of an. inert gas introduced through line it into catalyst eductor lll. Stripping with steam or inert gas may bedone to remove combustible, volatile contaminants. Screens or other means of effecting the separation of the coarse catalyst fraction' may be employed if desired. The amount of the` `practically 34% at 900 F.

catalyst so separated may be varied, depending on a number-o factors and in general, it may be within the range of about to 65% of the total catalyst. The amount oi' the fraction will be lower in a system of three or more separation stages than in a system with only two stages of separation. 'I'he catalyst separated in the rst stage may, for example, be about 80 to 200 mesh in the main, while the catalyst separated in the second stage may be 200 mesh and upward in a two-stage process. In another example with a nner catalyst, the rst stage may separate up to S mesh and the second stage, above 325 mesh. y

Leaving separator i9, the vapors carrying a finer tgaction of the suspended catalyst pass by line 2 to the second reactor 26 where further conversion takes place. By regulating the relative size of reactors i6 and 28, I may obtain any desired catalyst residence time (catalyst exposure time) with these fractions. The shape of the reactors is also important as it determines vapor velocity. Thus, in a given volume of reaction space, reactor i6 may be elongated to increase the vapor velocity and reduce sedimentation or it may be shortened and widened to decrease the vapor velocity and increase sedimentation or retarded settling, thereby increasing the residence time of the course catalyst without affecting the residence time of the ne catalyst which is carried through the reactor at substantially vapor velocity. The catalyst residence time, Which is the average length of time a given particle of catalyst is in contact with the vapors at reaction temperature in the reaction zone, will be greater for iower space velocities at a given rate of conversion. Conversion decreases with an increase in "space velocity. Thus, in order to maintain a given rate of conversion at high space velocity, it is necessary to use a short catalyst residence time. For example, at a space velocity of about 2.5 a catalyst residence time of 5 minutes will produce about 50% conversion of East Texas wide boiling range gas oil to gasoline at 900 F. With a residence time of 2 minutes, a "space velocity oi about 12 gave a conversion of "Space velocity is the volume of liquid oil per hour per volume (measured at rest) of catalyst in the reactor at any one instant. the space velocity and residence time for a one reactor system. The two or more stages of the system proposed herein will each contribute to the over all conversion and will therefore each have a combination of catalyst residence time, space velocity and temperature to give the conversion desired.

Reactor 26 is usually larger in diameter than reactor I6 to permit lower vapor velocity and longer residence time with the nner particles as a result of retarded settling. The vapors leaving reactor 26 carry the catalyst by line 21 into separator 28, which is more e'icient for separating iine catalyst than separator i9. The vapors, now substantially free of catalyst, pass by line 29 to fractionator 3l?. The catalyst separated in 28 passes through rotating feeder valve 3l to reservoir 32 and thence by line 33 to regeneration. The separated vapors free of catalyst are fractionated in iractionator 30 into a gasoiine and gas fraction which passes overhead by line @it leading to condenser and receiver 36. From the receiver the gas is conducted away by line 3l! and the gasoline is withdrawn by line tt.

The above gures apply to f The oil heavier than gasoline separated in iractionator 30 may be conducted by line 39 iuei or a part or all of it may be recycled by line 40 through heater #il and transfer line 42 baci; to the second stage reactor 26 where-the hot vapors serve to restore the temperature ci the reaction mixture. When operated in this Way the recycle oil vapors anrepreferably heated to a high'temperature before introducing them to said catalyst chamber. For example, a temperature between 1000 and 1150 F. may be employed.

The second stage reactor may, by this means, be maintained at a higher temperature than the first stage, thereby obtaining more complete utilization of the ilne catalyst. The higher carbon deposition from the recycle oil in 42 introduces less dilculty when deposited on the liner catalyst because its small dimensions facilitate burn` ing on regeneration.

The separated catalyst in lines 22 and 33 is conducted into regeneration chamber 43 where it is brought in contact with air or other oxygen-containing gas for the purpose of removing carbonaceous deposits with which it is contaminated. Air for this purpose is introduced by line 44 and an inert gas such as flue gas may be introduced by line 45. Regeneration is carried out at elevated temperatures of about 950 to 1200 F. and the regenerated catalyst is carried by the spent regeneration gases through line 46 back to catalyst hopper I1 where the catalyst is continually being withdrawn and returned to the cracking system. The temperature of regeneration may be controlled by air cpoling, by catalyst recycling, or other means. Carbon dioxide and other regeneration products are withdrawn by line 61 and they may be recycled to the regeneration chamber t3 for the purpose of controlling the temperature therein.

The pressure in my conversion system is usually near atmospheric but higher pressures may be employed, of the order of to 100 pounds per square inch and even somewhat higher, for example, 200 pounds per square inch. Varying the pressure has a pronounced effect on the sedimentation of catalystwith a given .throughput of oil. Increasing the pressure reduces vapor velocity and thereby permits greater sedimentation in the, reaction chambers. Excessive pressure is undesirable partly because ci an increase in catalyst contamination resulting from a higher rate of carbon deposition and partly because of a somewhat lower knock rating in the gasoline products.

Having thus described claim is:

l. 'Ihe process of conducting catalytic reactions in gaseous iiuids with the aid of suspended, solid contact catalysts consisting of particles of different sizes, which process comprises introducing said gaseous fluids into a vertical elongated reaction zone at the lower part thereof, maintaining said reaction zone at reaction temperature, dispersing finely divided catalysts in said gaseous fluid, maintaining said catalyst in suspension in said gaseous fluid within said reaction zone, ilowing said gaseous fluids upwardly through said reaction zone ,at a velocity suiiiciently low to provide for hindered settling of catalyst therein, withdrawing reaction products and catalyst at the upper part of said reaction zone, separating coarse catalyst from ne cata lyst and gaseous uid :from said reaction zone, conducting said gaseous fluid and iine catalyst to a second vertical reaction zene maintained at remy invention what I asians 3 action temperature, and therein eecting a turther reaction in said gaseous iluids in the presence oi' said ne catalyst, ilowing said gaseous duide upwardly through said second reaction zone at a velocity suillciently low to rovide for hindered settung of said une cstal st therein.

separating tine .catalyst from gasesMroin said second reaction sone, regenerating by combustion with air, both coarse and iine catalyst separated from said gaseous uids, recycling regenerated catalyst while hot to said reaction zone ilrst mentioned, and recovering the reaction products withdrawn from said second reaction sone.

2. In the process of converting hydrocarbon oils into gasoline of high knock rating by contacting the vapors of said oils with a iinely divided solid, porous contact catalyst of heterogeneous particle size suspended in said vapors ata conversion temperature, the improvement comprising dispersing the catalyst in oil vapors in a dispersion zone to produce a given desired ccncentration of catalyst in the vapors, passing said catalyst and vapors into a rst reaction zone ci relatively low vapor velocity wherein the vapors and catalyst flow upward, and the concentration oi catalyst is greater than in said dispersion zone and hindered sedimentation ot the coarse catalyst particles occurs. conducting the partially converted vapors and catalyst to'a separation zone where coarse catalyst particles are removed, conducting the remaining vapors andnnecatalyst particles to a second reaction zone where iurther conversion of oil vapors occurs, separating the remaining iine catalyst from said oil vapors and fractionating said oil vapors to proiduce the desiredy gasoline of high knock rating.

3. vihe process of claim 2 wherein the catalyst seated from the hydrocarbon vapors in both stages is regenerated by combustion with oxygentaining gas and recycled while hot to the nrs@ reaction zone.

t. Theprocess of converting hydrocarbon oils by the action of suspended solid catalysts in the vapor phase, comprising heating and vaporizing the oli at a high conversion' temperature. suspendingin the vapors of said oil a nnely divided catalyst consisting of a mixture of coarse and fr.. particles, effecting conversion of said oil in a drst conversion zone through which the -oil vapors' how upwardly with said catalyst mixture at relatively low velocity, thereby providing partial sedimentation of larger catalyst particles. separating the said larger catalyst particles from the mixture of catalyst and vapors, subjecting the remaining catalyst and vapors to further conversion in a second low velocity conversion zone, recovering the catalyst fromsaid vapors, fractionating and condensing the vapors to obtain desired hydrocarbon products regenerating the catalyst by controlled combustion and returning it while hot to the conversion system.

E. The process of converting hydrocarbon oils into gasoline of high knock rating which comprises subjecting the vapors o! said oils to the action of a solid siliceous catalyst in the form cia powder constituted ot non-uniform catalyst particle sizes, effecting partial conversion of the oil with said catalyst in an upfiowing stream in a rst conversion zone at sufficiently low vapor velocities to permit retarded settling of catalyst oi coarser particle size from said vapo s separating coarse catalyst from the remaini g catalyst and vapors, effecting fu er conversion of said oil vapors bythe action o the remaining catalystp4 ofilner particle size in a second conversion zon@ at lower vapor velocity, separating the ne catalyst from the vapors, recovering catalyst from both the coarse catalyst separation and the fine catalyst separation, regenerating said catalyst by combustion with oxygen-containing gas, whereby car-bonaceous deposits are removed therefrom and recycling said regenerated catalyst while hot into contact with said oil vapors iirst mentioned.

6. The process of converting higher boiling hydrocarbon oils into high knock rating gasoline by the action of suspended solid catalysts in the vapor phase. comprising suspending in the vapors of said oil at a high conversion temperature a finely divided catalyst of non-uniform particle size, effecting conversion of said oil in a conversion zone through which the oil vapors dow upwardly at relatively low velocity. thereby providing partial sedimentation of larger catalyst particles, separating the said larger catalyst particles from the mixture of catalyst and vapors. subjecting the remaining catalyst and vapors to further conversion in a vsecond low velocity conversion zone, recovering the catalyst from said vapors, separating from said `vapors the desired gasoline and a higher boiling distillate oil product, heating said higher boiling oil product to a high conversion temperature and returning it in regulated amounts to said second conversion zone.

7. The process of converting higher boiling hydrocarbon oils into high knock rating gasoline by the action oi' suspended solid catalysts in the vapor phase. comprising suspending in the vapors of said oilat a high conversion temperature a nely divided catalyst of non-uniform particle size, eiecting conversion 'of said oil in a conversion zone through which the oil vapors ilow upwardly at relatively low velocity, thereby providing partial sedimentation o! larger catalyst particles, separating the said larger catalyst par- 5 to said'second conversion zone.

8. The process of converting hydrocarbon oils by the action of suspended solid catalysts in the vapor phase, comprising suspending in the vapors of said oil at a high conversion temperature a iinely divided catalyst consisting of a mixture oi' coarse and fine particles, effecting conversion of said oil in a nrst vertical conversion zone through which the oil vapors flow upwardly with said mixture of coarse and ne catalyst at relatively low velocity, thereby providing .partial sedimentation of larger catalyst particles, separating lthe said larger catalyst particles from the mixture oi catalyst and vapors, subjecting the remaining fi'ne catalyst and vapors to further conversion by passing upwardly through a second low velocity vertical conversion zone at a higher temperature and a lower velocity than that of said first conversion zone, recovering the ne catalyst from vapors. fractionating and condensing the vapors to obtain desired hydrocarbon products, regenerating `the catalyst by controlled combustion and returning it while hotv to the conversion system.

VANDERVEER VOORHEES. 

